Tris(2,2,2-trifluoroethyl)borate [B(OCH2CF3)3] was found to be a mild and general reagent for the formation of a variety of imines by condensation of amides or amines with carbonyl compounds. N-Sulfinyl, N-toluenesulfonyl, N-(dimethylamino)sulfamoyl, N-diphenylphosphinoyl, N-(α-methylbenzyl), and N-(4-methoxyphenyl) aldimines are all accessible using this reagent at room temperature. The reactions are operationally simple, and the products are obtained without special workup or isolation procedures.

Promising levels of enantiocontrol are observed in the silanediol-catalyzed addition of silyl ketene acetals to benzopyrylium triflates. This rare example of enantioselective, intermolecular chromenone functionalization with carbonyl-containing nucleophiles has potential applications in the synthesis of bioactive chromanones and tetrahydroxanthones.

Enantiopure silanediols derived from BINOL are an innovative family of stereoselective hydrogen‐bond donor (HBD) catalysts. Silanediols incorporated into a BINOL framework are attractive catalysts, as they are readily accessible and highly customizable. Structural modifications of the BINOL backbone affect the reactivity and selectivity of the silanediol catalysts in the additions of silyl ketene acetals to N‐acyl isoquinolinium ions. The best results were obtained when the silanediol scaffold was substituted at the 4,4′‐ and 6,6′‐positions. This report includes details regarding the properties of selected BINOL‐based silanediol catalysts, including their acidities, binding constants, and X‐ray crystal structures.

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Sterically encumbered organosilanes can be difficult to synthesize with conventional, strongly basic reagents; the harsh reaction conditions are often low yielding and not suitable for many functional groups. As an alternative to the typical anionic strategies to construct silanes, the coupling of benzylic halides and arylhalosilanes with sonication has been identified as a high yielding and general strategy to access bulky and functionalized benzylic silanes. This new methodology provides a solution for the synthesis of families of bulky benzylic silanes for study in catalysis and other areas of chemical synthesis.